EP0330200B1 - Dispergierte Teilchen eines gehärteten Silikonmaterials enthaltende Fluorkautschukmischung - Google Patents

Dispergierte Teilchen eines gehärteten Silikonmaterials enthaltende Fluorkautschukmischung Download PDF

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Publication number
EP0330200B1
EP0330200B1 EP19890103188 EP89103188A EP0330200B1 EP 0330200 B1 EP0330200 B1 EP 0330200B1 EP 19890103188 EP19890103188 EP 19890103188 EP 89103188 A EP89103188 A EP 89103188A EP 0330200 B1 EP0330200 B1 EP 0330200B1
Authority
EP
European Patent Office
Prior art keywords
fluororubber
silicone material
composition
cured
parts
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP19890103188
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English (en)
French (fr)
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EP0330200A1 (de
Inventor
Keiji Yoshida
Masayuki Saito
Mitsuo Hamada
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DuPont Toray Specialty Materials KK
Original Assignee
Toray Silicone Co Ltd
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Publication date
Application filed by Toray Silicone Co Ltd filed Critical Toray Silicone Co Ltd
Publication of EP0330200A1 publication Critical patent/EP0330200A1/de
Application granted granted Critical
Publication of EP0330200B1 publication Critical patent/EP0330200B1/de
Expired legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/16—Homopolymers or copolymers or vinylidene fluoride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes

Definitions

  • the present invention relates to a fluororubber composition, and, more specifically, relates to a fluororubber composition which is highly suitable for blending or processing on a roll mill and which is readily released from molds during a molding operation.
  • Organic fluorine containing rubbers also referred to as fluororubbers
  • fluorororubbers are used in a broad range of industrial applications due to their excellent mechanical properties.
  • a shortcoming of these rubbers is the difficulty of fabricating them on roll mills and achieving a good release of the cured fluororubber from molds.
  • the molds have a definite tendency to become soiled during molding operations, which together with the poor release properties results in a high reject rate.
  • the continuous phase is a polyorganosiloxane and the dispersed phase is a fluorocarbon polymer.
  • the present invention was the result of extensive investigations directed at solving the aforementioned problems with fluororubbers.
  • the object of the present invention is to provide a fluororubber composition which is excellent with respect to its ability to be fabricated on roll mills and the low reject rate of articles molded from these compositions.
  • the present invention also provides a method for improving the processability of curable fluororubber compositions, specifically the ability of these compositions to be molded and fabricated using roll mills typically used for other types of rubber compositions.
  • the objective of the present invention is achieved by incorporating into a fluororubber from 0.1 to 30 weight parts per 100 weight parts of fluororubber of a finely divided particulate silicone material.
  • This invention provides an improved fluororubber composition
  • a fluororubber comprising 100 weight parts of a fluororubber and an amount of curing agent sufficient to cure said fluororubber, where the improvement comprises the presence in said composition of from 0.1 to 30 weight parts of a finely divided cured silicone material in the form of a rubber, gel or resin, where said silicone material exhibits an average particle diameter not exceeding 100 micrometers.
  • a method for improving the processability of a curable composition comprising 100 weight parts of a fluororubber and an amount of curing agent sufficient to cure said fluororubber, comprises combining said composition with from 0.1 to 15 weight parts of a finely divided cured silicone material in the form of a rubber, gel or resin, where said silicone material exhibits an average particle diameter not exceeding 100 micrometers.
  • the fluororubber compositions of this invention contain a curable fluorine-containing organic or fluorine-containing organosiloxane polymer as its main ingredient .
  • the cured polymer is a rubbery elastomer.
  • fluororubbers are described, for example, in the "Compendium of Synthetic Rubber Processing Technology. Fluororubber/Silicone Rubber.” [in Japanese] (Yuzuru Komeya, et al., authors, published by Kabushiki Kaisha Taisei-sha).
  • fluororubbers include but are not limited to (1) vinylidene fluoride-based polymers such as chlorotrifluoroethylene/-vinylidene fluoride copolymers, pentafluoropropene/vinylidene fluoride copolymers, and hexafluoropropene/vinylidene fluoride copolymers; and (2) fluorosilicone rubbers containing a fluoroalkyl group-containing organopolysiloxane as the main ingredient.
  • vinylidene fluoride-based polymers such as chlorotrifluoroethylene/-vinylidene fluoride copolymers, pentafluoropropene/vinylidene fluoride copolymers, and hexafluoropropene/vinylidene fluoride copolymers
  • fluorosilicone rubbers containing a fluoroalkyl group-containing organopolysiloxane as the main ingredient.
  • compositions of this invention typically include at least one of the conventional curing or vulcanizing agents for the fluorororubber ingredient.
  • Typical curing agents for the vinylidene fluoride-type of fluorororubbers include but are not limited to polyfunctional amines such as hexamethylenediamine carbamate and organoperoxides such as benzoyl peroxide and dicumyl peroxide, Curing agents for fluorosilicone rubbers include but are not limited to organoperoxides such as 2,4-dichlorobenzoyl peroxide, dicumyl peroxide and 2,5-dimethyl-2,5-di(t-butylperoxy)hexane.
  • the cured particulate silicone material of the present invention consists of particles or granules having average diameters not in excess of 100 micrometers.
  • the mechanical strength of the fluororubber composition of the present invention substantially declines when this average diameter of the particles exceeds 100 micrometers.
  • the concentration of particulate cured silicone material in the present compositions is from 0.1 to 30 weight parts, preferably from 0.1 to 15 weight parts, and most preferably from 0.1 to 5 weight parts per 100 weight parts of the fluororubber ingredient.
  • the ability of the particulate silicone material to function as a mold release agent is not apparent at concentrations below about 0.1 weight part, while the mechanical strength of the cured fluororubber can be adversely affected when the concentration of particulate silicone material exceeds about 30 weight parts.
  • the cured particulate silicone material can be a rubber, gel, or resin.
  • the silicone material which typically includes at least one organopolysiloxane, has been cured by an addition, condensation or free radical reaction.
  • Addition reaction-cured silicone materials are typically obtained by curing a composition comprising an organopolysiloxane having at least two silicon-bonded alkenyl groups per molecule, an organohydrogenpolysiloxane having two or more silicon-bonded hydrogen atoms per molecule, and a platinum-containing catalyst.
  • Organoperoxide-cured silicone materials are typically obtained heating an organopolysiloxane in the presence of an organoperoxide.
  • Condensation reaction-cured silicone materials are typically obtained by the curing a composition comprising a curing catalyst, an organopolysiloxane containing at least two silanol groups per molecule and, as the curing agent, an organohydrogenpolysiloxane or a silane containing at least three silicon-bonded hydrolyzable groups, such as alkoxy, per molecule.
  • Curing agents containing hydrolyzable groups typically require the presence of atmospheric moisture to activate them.
  • the curable silicone rubber composition can include additives, such as reinforcing fillers, to modify the physical properties of the cured material.
  • a preferred type of particulate silicone material is obtained by curing a silicone rubber composition in which at least a portion of the organic groups bonded to the silicon atoms of the organopolysiloxane are fluorinated propyl radicals.
  • the cured silicone material preferably contains an additive to improve compatibility or miscibility, and thereby improve the adhesion between the particulate silicone material and the fluororubber.
  • suitable additives of this type include but are not limited to fluoropropyl group-containing organoalkoxysilanes such as fluoropropyltrimethoxysilane and fluoropropylmethyl-dimethoxysilane; epoxy group-containing organoalkoxysilanes such as gamma-glycidoxypropyltrimethoxysilane, and gamma-glycidoxypropylmethyldimethoxysilane, partial hydrolysis condensates of any of these silanes, and epoxy group-containing organic compounds such as glycidyl methacrylate and vinylcyclohexene monoxide.
  • fluoropropyl group-containing organoalkoxysilanes such as fluoropropyltrimethoxysilane and fluoropropylmethyl-dimethoxysilane
  • epoxy group-containing organoalkoxysilanes such as gamma-glycidoxypropyltrimethoxysilane, and
  • One method for preparing the fluororubber composition of this invention comprises mixing the fluororubber, particulate cured silicone material and curing agent for the fluororubber to homogeneity using a two-roll mill.
  • the uncured fluororubber compositions of this invention excel with respect to their ability to be processed on roll mills typically used to for rubber compositions. Cured articles that have been molded using these compositions are readily released from molds without staining the mold surfaces, resulting a low reject rate for the finished articles.
  • the fluororubber composition to be evaluated was placed in a chromium-plated mold used to form key pads for electronic calculators.
  • the dimensions of the mold were 10 x 10 x 0.5 cm.
  • the composition was cured at 170 degrees Centigrade for 10 minutes. This molding process was repeated 100 times, and the mold-releasability was evaluated by visually examining the surfaces of the resultant key pads.
  • the percentage of moldings with rough and/or damaged surfaces was determined and is reported as the molding reject rate in the examples. It was observed that rough and/or damaged surfaces on the key pad were caused mainly by poor mold-release and/or soiling of the mold surfaces.
  • An addition reaction-curing silicone rubber composition was prepared from 100 parts of a dimethylvinylsiloxy-terminated dimethylpolysiloxane having a viscosity of (2x10 ⁇ 3 m2/second) (2,000 centistokes) and a vinyl content of 0.25%, 1.5 parts of a trimethylsiloxy-terminated methylhydrogenpolysiloxane having a viscosity of (1x10 ⁇ 5 m2/second) (10 centistokes) and a silicon-bonded hydrogen atom content of 0.9%, and 0.15 parts of 3% isopropanolic chloroplatinic acid solution. 5 Parts of a nonionic surfactant available as Tergitol® TMN-6 from Union Carbide Corporation and 200 parts water were then added and mixed into this silicone rubber composition.
  • a nonionic surfactant available as Tergitol® TMN-6 from Union Carbide Corporation and 200 parts water were then added and mixed into this silicone rubber composition.
  • the resultant aqueous dispersion of a curable silicone rubber composition was cured by introducing the dispersion into 5000 parts of water maintained at a temperature of 70° C.
  • the cured silicone rubber was then isolated and dried by heating to yield a particulate silicone rubber with an average particle diameter of 10 micrometers.
  • a curable fluororubber composition of this invention was obtained by kneading the following ingredients to homogeneity on a two-roll mill: 4 parts of the particulate silicone rubber prepared as described in the preceding paragraph, 100 parts of a vinylidene fluoride-type fluororubber (Viton(R) E430 from E.I. DuPont Company), 3 parts calcium hydroxide, 6 parts magnesium oxide, 25 parts carbon black, and 2 parts dicumyl peroxide.
  • This fluororubber composition did not substantially adhere to the surface of the mill rolls, and was judged to have a good roll-workability.
  • the reject rate for the molded articles was 11%, and the mold-releasability in this test was excellent.
  • a fluororubber composition was prepared as described in the preceding portion of this example, with the exception that the cured particulate silicone rubber was not added.
  • This fluororubber composition readily adhered to the surface of the mill rolls, and was therefore considered to have poor roll-workability.
  • the reject rate for molded articles prepared from this composition was 21%.
  • a condensation reaction-curing silicone rubber composition was prepared from 100 parts of a dimethylhydroxysiloxy-terminated dimethylpolysiloxane having a viscosity of (1x10 ⁇ 4 m2/second) ((100 centistokes) 10 parts of the methylhydrogenpolysiloxane described in Example 1, 10 parts gamma-glycidoxypropyltrimethoxysilane to improve the compatibility of the silicone rubber with the fluororubber, and 1 part of stannous octoate as the curing catalyst.
  • the composition was cured as described in Example 1 to yield particles of cured silicone rubber exhibiting an average diameter of 12 micrometers.
  • a curable fluororubber composition of this invention 5 parts silicone rubber powder obtained as described in the first section of this example, 100 parts of a vinylidene fluoride-type fluororubber (Dai-el G901 from Daikin Kogyo Co., Limited), 2 parts dicumyl peroxide, 4 parts triallyl isocyanurate, and 20 parts carbon black.
  • This fluororubber composition had an excellent roll-workability during blending. When the composition was molded , the cured articles released easily from the mold and the reject rate was 8%.
  • a fluororubber composition of this invention was prepared by blending the following ingredients to homogeneity on a two-roll mill: 5 parts of a cured particulate silicone rubber prepared as described in Example 2, 100 parts of a fluorosilicone rubber (LS63u from Toray Silicone Company Limited), and 1 part of 2,5-dimethyl-2,5-di(t-butylperoxy)hexane.
  • the curable composition could be processed on a roll mill without difficulty. Cured articles molded using this composition did not stick to or stain the mold surfaces.
  • a finely divided addition reaction-curing fluorosilicone rubber of this invention was prepared from 100 parts dimethylvinylsiloxy-terminated trifluoropropylmethylsiloxane- dimethylsiloxane copolymer having a vinyl group content of 0.15% and containing 60 mole% of trifluoropropylmethylsiloxane units and 40 mole% dimethylsiloxane units); 1 part of the methylhydrogenpolysiloxane described in Example 1, and 0.15 parts of a 3% isopropanolic chloroplatinic acid solution.
  • the resultant fluorosilicone rubber composition was cured as described for the finely divided material of Example 1 to yield a powder consisting essentially of spherical particles with average diameters of 10 micrometers.
  • a curable fluororubber composition was prepared using the procedure of Example 2, with the modification that the fluorosilicone rubber powder prepared as described in the preceding section of the present example was used in place of the silicone rubber powder described in Example 2.
  • the resultant composition exhibited a good ability to be blended on the roll mill.
  • the reject rate for the articles molded from this composition was 5%.
  • a silicone rubber powder was prepared using the procedure described in Example 2, with the modification that trifluoropropyltrimethoxysilane was used in place of the gamma-glycidoxypropyltrimethoxysilane used in Example 2.
  • a curable fluororubber composition was then prepared using the procedure of Example 2, with the modification that the silicone rubber powder obtained as described in the preceding paragraph of the present example above was used in place of the silicone rubber powder described in Example 2. Evaluation of this composition demonstrated its excellent roll-workability, molding properties, and a molding reject rate of 3%.
  • a silicone rubber powder was prepared according to the procedure of Example 1, but without the surfactant described in Example 1.
  • the cured silicone rubber consisted of particles with an average diameter of 20 micrometers.
  • a fluororubber composition was prepared according to the procedure in Example 1, with the modification that the silicone rubber powder described in the first paragraph of the present example was used in place of the silicone rubber powder of Example 1.
  • the composition exhibited excellent workability on the roll mill and releasability from the mold.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (5)

1. Fluorkautschukzusammensetzung, umfassend
(A) 100 Gewichtsteile härtbaren Fluorkautschuk und
(B) eine Menge eines Härtungsmittels, die ausreicht, um den Fluorkautschuk zu härten,
wobei die Verbesserung darin besteht, daß weiterhin
(C) 0,1 bis 30 Gewichtsteile feinverteiltes gehärtetes Silikonmaterial in Form eines Kautschuks, Gels oder Harzes vorhanden sind, wobei das Silikonmaterial einen durchschnittlichen Teilchendurchmesser aufweist, der nicht größer ist als 100 µm.
2. Zusammensetzung nach Anspruch 1, worin das gehärtete Silikonmaterial weiterhin ein Additiv enthält, ausgewählt aus Epoxygruppen enthaltenden Organoalkoxysilanen, Teilhydrolysekondensaten davon, Fluorpropylgruppen enthaltenden Organoalkoxysilanen und Teilhydrolysekondensaten davon.
3. Zusammensetzung nach Anspruch 1, worin das feinverteilte Silikonmaterial hergestellt wird durch Vermischen eines härtbaren Silikonkautschuks mit Wasser und einem oberflächenaktiven Mittel in einer Kolloidmühle oder einem Homogenisator unter Bildung einer wäßrigen Dispersion und Härten der entstehenden Dispersion, indem sie mit Wasser, das auf eine Temperatur von mindestens 50°C erhitzt wurde, gemischt wird.
4. Zusammensetzung nach Anspruch 1, worin der Fluorkautschuk Fluorsilikonkautschuk ist.
5. Zusammensetzung nach Anspruch 1, worin der Fluorkautschuk ein organischer Fluorkautschuk ist.
EP19890103188 1988-02-24 1989-02-23 Dispergierte Teilchen eines gehärteten Silikonmaterials enthaltende Fluorkautschukmischung Expired EP0330200B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP41553/88 1988-02-24
JP4155388A JPH01215847A (ja) 1988-02-24 1988-02-24 ふっ素系ゴム組成物

Publications (2)

Publication Number Publication Date
EP0330200A1 EP0330200A1 (de) 1989-08-30
EP0330200B1 true EP0330200B1 (de) 1992-07-15

Family

ID=12611618

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19890103188 Expired EP0330200B1 (de) 1988-02-24 1989-02-23 Dispergierte Teilchen eines gehärteten Silikonmaterials enthaltende Fluorkautschukmischung

Country Status (5)

Country Link
EP (1) EP0330200B1 (de)
JP (1) JPH01215847A (de)
AU (1) AU617423B2 (de)
CA (1) CA1339433C (de)
DE (1) DE68902065T2 (de)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2794296B2 (ja) * 1988-08-10 1998-09-03 エヌオーケー株式会社 成形品
JP2686787B2 (ja) * 1988-10-17 1997-12-08 東レ・ダウコーニング・シリコーン株式会社 ふっ素系ゴム組成物
JP2854871B2 (ja) * 1989-01-26 1999-02-10 東レ・ダウコーニング・シリコーン株式会社 ふっ素系ゴム組成物
JP2693691B2 (ja) * 1992-07-31 1997-12-24 信越化学工業株式会社 シリコーンゴム硬化物の再利用方法
JPH0741627A (ja) * 1993-07-28 1995-02-10 Toray Dow Corning Silicone Co Ltd ゴム組成物
US5480930A (en) * 1994-08-18 1996-01-02 Dow Corning Corporation Fluorocarbon rubbers modified by silicone resins
EP1995277A4 (de) * 2006-03-15 2011-07-06 Daikin Ind Ltd Verbundwerkstoff aus fluorkautschuk, kraftstoffpermeationsresistentes dichtungselement daraus und verfahren zur herstellung eines derartigen verbundwerkstoffes
WO2016031242A1 (ja) * 2014-08-29 2016-03-03 東レ・ダウコーニング株式会社 フッ素含有重合体－フッ素含有オルガノポリシロキサン複合材料、その製造方法、その用途、及びその製造方法に用いる前駆体組成物
CN111073303A (zh) * 2019-12-05 2020-04-28 宁国天运橡塑制品有限公司 疏水氟硅橡胶密封垫的制备方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1076115A (en) * 1963-10-03 1967-07-19 Bendix Corp Rubbery compositions and method of making them
US3415900A (en) * 1964-01-10 1968-12-10 Minnesota Mining & Mfg Cross linking hydrofluorinated olefin polymers and silicone rubbers and resultant cross linked compositions
JPS62243621A (ja) * 1986-04-17 1987-10-24 Toray Silicone Co Ltd シリコ−ンゴム粒状物の製造方法

Also Published As

Publication number Publication date
EP0330200A1 (de) 1989-08-30
AU617423B2 (en) 1991-11-28
DE68902065D1 (de) 1992-08-20
DE68902065T2 (de) 1993-02-25
JPH01215847A (ja) 1989-08-29
AU3024689A (en) 1989-08-24
CA1339433C (en) 1997-09-02

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